EP2253656B1 - Method of enhancing conductivity of conductive polymer - Google Patents
Method of enhancing conductivity of conductive polymer Download PDFInfo
- Publication number
- EP2253656B1 EP2253656B1 EP20080720419 EP08720419A EP2253656B1 EP 2253656 B1 EP2253656 B1 EP 2253656B1 EP 20080720419 EP20080720419 EP 20080720419 EP 08720419 A EP08720419 A EP 08720419A EP 2253656 B1 EP2253656 B1 EP 2253656B1
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- EP
- European Patent Office
- Prior art keywords
- conductive polymer
- polymer product
- water
- conductivity
- carbon dioxide
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001940 conductive polymer Polymers 0.000 title claims description 118
- 238000000034 method Methods 0.000 title claims description 37
- 230000002708 enhancing effect Effects 0.000 title claims description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 124
- 239000001569 carbon dioxide Substances 0.000 claims description 62
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 42
- 239000003960 organic solvent Substances 0.000 claims description 35
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- -1 poly(p-phenylene) Polymers 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 15
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 15
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 14
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 229920000767 polyaniline Polymers 0.000 claims description 7
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000889 atomisation Methods 0.000 claims description 4
- 229920003026 Acene Polymers 0.000 claims description 3
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 229920000553 poly(phenylenevinylene) Polymers 0.000 claims description 3
- 229920001197 polyacetylene Polymers 0.000 claims description 3
- 229920002098 polyfluorene Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- 230000008016 vaporization Effects 0.000 claims 1
- 239000000047 product Substances 0.000 description 122
- 239000002245 particle Substances 0.000 description 17
- 239000006185 dispersion Substances 0.000 description 8
- 229920000144 PEDOT:PSS Polymers 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 4
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- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
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- 239000002253 acid Substances 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 150000003233 pyrroles Chemical class 0.000 description 1
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/514—Electron transport
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249986—Void-containing component contains also a solid fiber or solid particle
Definitions
- the present invention relates to a method of enhancing the conductivity of a conductive polymer product, more particularly to a method of further enhancing the conductivity of a conductive polymer product obtained by polymerizing 3,4-ethylenedioxythiophene in an aqueous solution of polystyrenesulfonic acid.
- EP 2 158 975 A1 relates to a method for producing a conductive polymer film suitable for enhancing the electrical conductivity of a PEDOT/ PSS film by drying.
- US 2005/029117 A1 deals with the electrochemical synthesis of electrically conductive polymers in supercritical fluids.
- US 6156 235 A relates to an in-situ vapor phase polymerizatian of pyrroles for producing a conductive elastomeric foam.
- WO 98/43250 A1 describes forming a conductive polymer by polymerizing a monomer in supercritical carbon dioxide.
- WO 2005/071696 A1 relates to a method for deposition of a conductive polymer coating on an insulating substrate using liquid or supercritical carbon dioxide as a solvent in two steps: After a monomer is caused to impregnate the substrate as textile fibers, an in-situ oxidative polymerization of monomers is performed.
- WO 2004/091571 A2 relates to polymer coating of nanoparticles using a supercritical antisolvent process.
- Polymerization of 3,4-ethylenedioxythiophene in an aqueous solution of polystyrenesulfonic acid provides a conductive polymer product which is a mixture of polystyrene sulfonic acid and poly(3,4-ethylonedioxythlophene).
- This type of conductive polymer products is sold as Baytron, a registered trademark (See non-patent documents 1 and 2.).
- a product sold as Baytron P, "Baytron” of which is a registered trademark has a conductivity of 1 S/cm. It is known that this product with a 5% DMSO added has an enhanced conductivity of 80 S/cm (See non-patent documents 1 and 2.).
- compositions in order to have the market recognize these compositions as a replacement for ITO, it is desirable that they have more excellent properties than ITO. In other words, a new technology to further enhance the conductivity of these conductive polymer products is desired.
- An objective of the present invention is to provide a method of further enhancing the conductivity of various conductive polymer products including a conductive polymer product prepared through polymerization of 3,4-ethylenedioxythiophene in an aqueous solution of polystyrenesulfonic acid.
- the present invention provides the following means:
- the means recited in claim 1 is a method of enhancing a conductivity of a conductive polymer product comprising placing a conductive polymer product, which is a mixture of polystyrene sulfonic acid and poly (3,4-ethylenedioxythiophene), or a conductive polymer selected from the group consisting of polyacetylene, poly(p-phenylene), poly(phenylene vinylene), polypyrrole, poly(3-methylthiophene), polyaniline, polythiophene, poly(thienylene vinylene), polyfluorene, and polyacene, water, an organic solvent compatible with the conductive polymer product, and carbon dioxide gas in a pressure vessel; and applying heat and pressure to an interior of the pressure vessel to bring the carbon dioxide into a supercritical state and maintaining the supercritical state of carbon dioxide in the presence of water for a predetermined time period.
- a conductive polymer product which is a mixture of polystyrene sulfonic acid and poly (3
- the means recited in claim 2 is the method of enhancing a conductivity of a conductive polymer product according to claim 1, wherein the conductive polymer product is made through bonding of poly 3,4-ethylenedioxythiophene with SO 3 -groups included in the molecules of polystyrenesulfonic acid and swells in water to form a water-swollen polymer product.
- the means recited in claim 3 is the method of enhancing a conductivity of a conductive polymer product according to claim 1 or 2, wherein the organic solvent is at least one selected from the group consisting of dimethyl sulfoxide, ethylene glycol, N-methylpyrrolidone and N,N-dimethylformamide.
- the means recited in claim 4 is the method of enhancing a conductivity of a conductive polymer product according to any one of claims 1-3, wherein the interior of the pressure vessel is pressurized to a pressure from 7 to 25 MPa and heated to a temperature from 85 to 110°C, and the pressure and the temperature are maintained for 0.5 to 4 hours.
- the present invention is capable of providing a method of further enhancing a conductivity of conductive polymer products themselves including a polymer product obtained by polymerizing3,4-ethylenedioxythiophene in an aqueous solution of polystyrenesulfonic acid, and/or polyaniline.
- the method of enhancing conductivity includes a step of placing in a pressure vessel a conductive polymer product, which is obtained by polymerizing 3,4-ethylenedioxythlophone in an aqueous solution of polystyrenesulfonic acid, and/or polyaniline; water; an organic solvent compatible with the conductive polymer product; and carbon dioxide gas, which is followed by a step of applying heat and pressure to the interior of the pressure vessel to bring the carbon dioxide gas into a supercritical state.
- a conductive polymer product which is obtained by polymerizing 3,4-ethylenedioxythlophone in an aqueous solution of polystyrenesulfonic acid, and/or polyaniline
- water an organic solvent compatible with the conductive polymer product
- carbon dioxide gas which is followed by a step of applying heat and pressure to the interior of the pressure vessel to bring the carbon dioxide gas into a supercritical state.
- the conductive polymer product includes polystyrenesulfonic acid and poly(3,4-ethylenedloxy-thiophene). This conductive polymer product is not merely a blend of polystyrenesuffonle acid and poly(3,4-ethylenedioxy- thiophene). The product is considered to have a structure where poly(3,4-ethylenedioxythiophene) is coordinated by -SO 3 - moieties of polystyrenesulfonic acid.
- This type of conductive polymer products is sold as Baytron, which is a product name.
- Examples of the conductive polymer products capable of being used for the method of the present invention may include Baytron® P, Baytron® PAG, Baytron® PH, Baytron® PTP, Baytron® PLS, Baytron® PHS and Baytron® PHCV4.
- conductive polymers such as polyacetylene, poly(p-phenylene), poly(phenylene vinylene), polypyrrole, poly(3-methylthiophene), polyaniline, polythiophene, poly(thienylene vinylene), polyfluorene, and polyacene.
- These conductive polymers after a treatment by the method of enhancing conductivity according to the present invention have a smaller particle size than the polymers before the treatment.
- a sure theoretical base has not been established, it is supposed that the smaller particle size of the conductive polymer products shortens the path along which electrons move, whereby conduction is caused, in conduction within a molecular chain, conduction between molecular chains and conduction between particles.
- Examples of the water to be mixed with the conductive polymer product may include ion-exchanged water and extrapure water.
- the proportion of water to the conductive polymer product in the pressure vessel is generally from 50 to 10000 parts by mass, preferably from 20 to 2000 parts by mass, to the part by mass of the conductive polymer product.
- the conductive polymer product may float on or in the water at a level corresponding to an upper part of the vessel, which does not let the reaction take place.
- the amount of water is too small, the reaction may not proceed sufficiently.
- the use of water in an amount less than the range suffers from another disadvantage: A dispersing and atomizing operation takes moisture from the conductive polymer product and turns it dry, which makes it shrivel.
- the use of water in an amount more than the range also has another disadvantage: The concentration of the treated product dispersed in water is very small, which makes it impossible to use the dispersion as it is and requires adjustment of the concentration of the dispersion.
- a Baytron itself is a water dispersion including a conductive polymer product in an amount from 1 to 1.3% by mass. Therefore when a Baytron is used as conductive polymer product, the proportion of water to a Baytron may be generally from 0.5 to 3 parts by volume, preferably from 1 to 2 parts by volume, to the part by volume of the Baytron.
- organic solvent compatible with the conductive polymer product may include ethylene glycol, N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone.
- the amount of the organic solvent should be decided so that the proportion of the organic solvent to a mixture of water and the conductive polymer product is generally from 1 to 10% by mass, preferably from 3 to 6% by mass.
- the amount of the organic solvent is less than the range, an improvement in conductivity cannot be expected.
- the amount of the solvent exceeds the range, the treated product being applied to an intended use may fall under the influence of an excessive amount of additives and may be incapable of forming a film.
- Another example of the influence is that when an article is coated with the treated product, a film of the product may become uneven or smooth coating of the article may not be carried out.
- the proportion of carbon dioxide to water in the pressure vessel is normally from 80 to 500 grams of carbon dioxide, preferably from 95 to 400 grams thereof, to 10 ml of water.
- the method of this invention requires introducing carbon dioxide, water, the conductive polymer product and the organic solvent into a pressure vessel.
- a pressure vessel There is no limitation on the order of introducing carbon dioxide, water, the conductive polymer product and the organic solvent into the pressure vessel. It may be acceptable if the conductive polymer product, the organic solvent and water are mixed prior to the introduction of them into the pressure vessel and afterward the resultant mixture is placed in the pressure vessel.
- water, the conductive polymer product and the organic solvent are placed in a pressure vessel first. Subsequently carbon dioxide gas is injected into the pressure vessel. Then, the conditions inside the pressure vessel are turned to those which bring carbon dioxide into a supercritical state. Specifically, the interior of the pressure vessel is kept at a pressure normally from 7 to 25 MPa, preferably from 9 to 15 MPa, and a temperature normally from 85 to 110°C, preferably from 95 to 105°C. Also, the time period to keep carbon dioxide in the pressure vessel in a supercritical state is normally from 0.5 to 3 hours, preferably from 1 to 2 hours. There is no special limitation on the shape of the pressure vessel as long as carbon dioxide is capable of being brought into a supercritical state in the vessel.
- the pressure vessel may be in the shape of, for example, a tank or a tube such as a straight tube and a hose.
- the pressure inside the vessel is returned to normal pressure.
- the carbon dioxide in the pressure vessel is then released to the atmosphere.
- a mixture of the water, the conductive polymer product and the organic solvent thus remains in the pressure vessel.
- the mixture may be used as it is in some applications.
- the product may be separated from the remaining by an ordinary separator such as a filter.
- the method of the present invention turns the pretreated conductive polymer product to an inventive conductive polymer product in the shape of small particles.
- the resultant product has an average particle size from 0.02 to 0.05 ⁇ m.
- the average particle size of an obtained product may be measured with a particle size distribution analyzer, such as a "Microtrac", a product of Nikkiso Co., Ltd.
- a conductive polymer product to which the method of the present invention is applied is a mixture of polystyrenesulfonic acid and poly(3,4-ethylenedioxythiophene)
- the conductive polymer product swells with water to form a water-swollen polymer product, which is made possible by the fact that the molecules of the polystyrenesulfonic acid, included in the conductive polymer product, have -SO 3 - groups capable of forming electrovalent bonds with the poly(3,4-ethylenedioxythiophene).
- This water-swollen polymer product has ionic functional groups -SO 3 - in the molecules thereof, which are capable of bonding with water molecules, thereby we think swelling the polymers with water.
- this conductive polymer product is placed in a pressure vessel and the method according to the present invention is applied to the product, i.e. carbon dioxide is brought into a supercritical state in the presence of water and the conductive polymer product
- the supercritical carbon dioxide has a density close to a density of the gas while keeping the properties of liquid, which brings the supercritical carbon dioxide into a state in which it easily permeates into polymers.
- the carbon dioxide permeates into and passes through the polymer molecules, water molecules penetrate into the polymer molecules together with the carbon dioxide. Thereafter, the pressure in the pressure vessel is returned to normal pressure, which results in the situations where the carbon dioxide vaporizes in a moment and the volume of the water increases.
- the water with an increased volume remaining in the polymer molecules after the carbon dioxide in the form of gas escapes from the molecules cuts principal chains of the polymers to form a conductive polymer product in the shape of fine particles. It is supposed that the cutting of the principal chains contributes to atomization of a conductive polymer product which is placed in a pressure vessel to receive the treatment.
- conductive polymer products treated by the method exhibit a remarkably enhanced conductivity compared with those before the treatment.
- the resistance of a conductive polymer product after the treatment by the method of the invention is 1/10th or less than 1/10th as large as that of the conductive polymer product before the treatment.
- Figure 1 shows a schematic illustration of an apparatus for enhancing conductivity, an example suitable to carry out the present invention.
- the apparatus for enhancing conductivity 1 includes a pressure vessel 2, a carbon dioxide cylinder 3, a water tank 4 and a third valve 5.
- the pressure vessel 2 should be a vessel capable of containing a conductive polymer product obtained by polymerizing 3,4-ethylenedioxythiophene in an aqueous solution of polystyrenesulfonic acid; water; an organic solvent compatible with the conductive polymer composition; and carbon dioxide, and capable of bringing carbon dioxide into a supercritical state.
- the pressure vessel 2 should be equipped with a stirrer 2A for stirring the contents therein.
- the third manual valve 5 is placed in an exhaust pipe attached to the pressure vessel 2.
- Carbon dioxide gas is stored in the carbon dioxide cylinder 3, and is supplied to the pressure vessel 2 from the cylinder.
- the carbon dioxide cylinder 3 is placed prior to the pressure vessel 2, and communicates with the vessel.
- a first pump 3A and a first valve 3B are arranged in this order.
- Pure water is stored in the water tank 4 and supplied to the pressure vessel from this tank.
- the water tank 4 is placed prior to the pressure vessel 2 and communicates with the vessel. Between the water tank 4 and the pressure 2 are arranged a second pump 4A and a second valve 4B in this order.
- a predetermined amount of a conductive polymer product and a predetermined amount of an organic solvent are introduced into the pressure vessel 2. (See Figure 2(A) .)
- the second pump 4A and the second valve 4B are also activated, so that pure water is supplied from the water tank 4 to the pressure vessel 2. (See Figure 2 (C) .) Either the pure water or the carbon dioxide gas may be supplied earlier than the other, or they may be supplied simultaneously.
- the pressure and the temperature inside the pressure vessel 2 are raised, which brings the supplied carbon dioxide gas into a supercritical state. If necessary, additional carbon dioxide gas is forced into the pressure vessel 2.
- the stirrer 2A may be actuated, at the operator's discretion, to stir the carbon dioxide to be or being in a supercritical state and the pure water. (See Figure 2 (D) .) Thereafter the carbon dioxide is kept in a supercritical state for a predetermined time period. (See Figure 2(E) .)
- the third valve 5 is operated, so that the carbon dioxide in a gaseous state is released from the pressure vessel 2 through the third valve 5 to the atmosphere.
- the pressure inside the pressure vessel 2 is thus reduced and returned to normal pressure.
- Water, the organic solvent and the treated conductive polymer product remain in the pressure vessel 2.
- the resultant conductive polymer product is separated and collected from the mixture of the water, the organic solvent and the treated conductive polymer product in the pressure vessel 2 by a separator.
- FIG. 1 One example is shown in Figure 3 .
- a second pressure vessel 6 is placed downstream from the valve 3B, connected to the valve with a pipe.
- the inside of the second pressure vessel 6 communicates with the first pressure vessel 2 through a pipe provided with a fourth valve 7.
- a coil reactor 8, which is a tubular reactor wound in the shape of a coil, is placed downstream from the first pressure vessel 2 and connected thereto through a pipe.
- a pipe branching off from the pipe that connects the first pressure vessel 2 with the coil reactor 8 is connected to a pipe extending from the second valve 4B, so that water stored in the water tank 4 is capable of being supplied to the coil reactor 8.
- the operation of the apparatus for enhancing conductivity 1 begins by supplying carbon dioxide gas from the carbon dioxide cylinder 3 to the second pressure vessel 6, and heating the inside of the second pressure vessel 6 to a predetermined temperature so that the carbon dioxide is brought into a supercritical state in the second pressure vessel 6. Meanwhile the first pressure vessel 2 is charged with predetermined amounts of a conductive polymer product and an organic solvent. Then carbon dioxide in a supercritical state supplied from the second pressure vessel 6 is introduced into the first pressure vessel 2, where the conductive polymer product is allowed to contact the supercritical carbon dioxide as well as the organic solvent.
- a mixture of the supercritical carbon dioxide, the conductive polymer product and the organic solvent is fed to the coil reactor 8, while water in the water tank 4 is supplied via the valve 4B in an open state to the coil reactor 8.
- the supercritical carbon dioxide, the conductive polymer product, water and the organic solvent in a state of a mixture pass through the coil reactor 8. While they are passing through the coil reactor 8, the atomization and conductivity-enhancement of the conductive polymer are achieved.
- the length of the coil of the coil reactor 8 and the inner diameter thereof are decided so that the reactor is capable of containing the mixture for a period of time necessary to achieve atomization and conductivity enhancement of the conductive polymer product. Also, the flow rate of the fluid flowing in the coil is decided suitably.
- the interior of the pressure vessel 2 was heated to 100°C, and 308 g of carbon dioxide gas was forced into the pressure vessel 2 so that the interior had a pressure of 10 MPa.
- the carbon dioxide gas that had been supplied to the pressure vessel 2 was thus brought into a supercritical state.
- the operator actuated a stirrer 2A to stir the carbon dioxide to be or being in the supercritical state and water at his/her discretion. Then, the carbon dioxide fluid in the supercritical state was kept for one hour.
- the third valve 5 was operated and the pressure inside the pressure vessel 2 was returned to normal pressure.
- a mixture of water, DMSO and a treated conductive polymer product remained in the vessel 2.
- the mixture was taken out of the pressure vessel 2.
- the mixture was used in the form of an aqueous dispersion, the mixture was not subjected to any further treatment.
- the resultant was used in the form of particles, the mixture was subjected to filtration. The treated conductive polymer product was thus collected.
- the particle size distribution of the particles of the conductive polymer product before they were placed in the pressure vessel 2 was measured with the particle size distribution analyzer, specifically a device named "Microtrac” produced by Nikkiso Co., Ltd.
- the conductivity of the collected conductive polymer product was evaluated. Specifically, the resistance of the product was measured with a surface resistance meter. As a result, the surface resistance was 0.607 x 10 3 ⁇ / ⁇ . The surface resistance of the conductive polymer product before the treatment was 10 6 ⁇ / ⁇ .
- the 1 wt% aqueous dispersion of the conductive polymer product (product name: Baytron P) used in Working Example 1 in an amount of 10 mL and DMSO in an amount of 1.1 g were mixed. The mixture was dried at temperatures from 50 to 100°C. Then a film of the resultant was formed. The conductivity of the resulting conductive polymer product was measured with the same method as in Working Example 1. The surface resistance was 10 4 ⁇ / ⁇ .
- the method of enhancing conductivity according to the present invention is capable of dramatically reducing the surface resistance of a treated conductive product.
- the method of the present invention is capable of remarkably enhancing the conductivity of a conductive product.
- the conductive polymer product treated by the method of the present invention is atomized, which improves smoothness of the surface of a film formed from the treated product.
- the resultant conductive polymer product, with its advantages of the smoothness utilized, may suitably be applied to electrodes of conductive polymer aluminum solid capacitors and organic electroluminescence.
- the surface resistance of the Baytron PHCV4 conductive polymer product after the treatment was measured with the same method as in Working Example 1. The measured value was 200 ⁇ / ⁇ . The surface resistance of the product before the treatment was 0.227 x 10 4 ⁇ / ⁇ .
- the surface resistance of the Baytron PHCV4 conductive polymer product after the treatment was measured with the same method as in Working Example 1.
- the surface resistance was 10 3 ⁇ / ⁇ .
- the results were as follows: The conductivity of the conductive polymer product produced in Working Example 5 where the organic solvent was NMP was evaluated as 0.830 x 3 ⁇ / ⁇ . The conductivity, or the surface resistance, of the conductive polymer product produced in Working Example 3 where the organic solvent was ethylene glycol was evaluated as 1.093 x 10 3 ⁇ / ⁇ . It can be said that DMSO is preferable as organic solvent based on the results of Working Examples 4, 5 and 6.
- Working Example 7 the same steps as those of Working Example 1 were carried out, except that 10 mL of a 4-8 wt% aqueous dispersion of polyaniline was used in place of 10 mL of the 1 wt% dispersion of the conductive polymer product (product name: Baytron P).
- Working Examples 8 and 9 the same steps as those of Working Examples 2 and 3 were respectively carried out, with the same change as in Working Example 7.
- DMSO is preferable as organic solvent. It was also proven that the method using polyaniline is also capable of enhancing conductivity.
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- Processes Of Treating Macromolecular Substances (AREA)
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JP2008060106A JP5243067B2 (ja) | 2008-03-10 | 2008-03-10 | 導電性ポリマーの導電性向上方法 |
PCT/JP2008/000533 WO2009113125A1 (ja) | 2008-03-10 | 2008-03-11 | 導電性ポリマーの導電性向上方法 |
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EP2253656A1 EP2253656A1 (en) | 2010-11-24 |
EP2253656A4 EP2253656A4 (en) | 2011-09-28 |
EP2253656B1 true EP2253656B1 (en) | 2014-05-14 |
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EP20080720419 Not-in-force EP2253656B1 (en) | 2008-03-10 | 2008-03-11 | Method of enhancing conductivity of conductive polymer |
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US (1) | US8188212B2 (ja) |
EP (1) | EP2253656B1 (ja) |
JP (1) | JP5243067B2 (ja) |
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JP5377303B2 (ja) * | 2007-06-18 | 2013-12-25 | 英夫 吉田 | 導電性高分子の被膜製造方法 |
JP5041606B2 (ja) * | 2009-10-02 | 2012-10-03 | 日機装株式会社 | リチウムイオン二次電池における改質微粉状正極物質の製造方法 |
JP5008153B2 (ja) * | 2009-10-26 | 2012-08-22 | 日機装株式会社 | リチウムイオン二次電池における改質微粉状正極物質の製造方法 |
JP5740925B2 (ja) * | 2010-11-15 | 2015-07-01 | ナガセケムテックス株式会社 | 導電性コーティング組成物及び積層体 |
CN104059432B (zh) * | 2013-03-20 | 2016-01-06 | 北京阿格蕾雅科技发展有限公司 | 透明碳纳米管高分子复合导电墨水及其制备方法 |
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US5855819A (en) | 1997-03-27 | 1999-01-05 | University Of North Carolina At Chapel Hill | Synthesis of conductive polymers in liquid and supercritical CO2 |
US6156235A (en) * | 1997-11-10 | 2000-12-05 | World Properties, Inc. | Conductive elastomeric foams by in-situ vapor phase polymerization of pyrroles |
US6890584B2 (en) * | 2000-06-28 | 2005-05-10 | Agfa-Gevaert | Flexographic ink containing a polymer or copolymer of a 3,4-dialkoxythiophene |
JP4144778B2 (ja) * | 2001-11-06 | 2008-09-03 | 国立大学法人東京工業大学 | イオン伝導性高分子およびその製造方法ならびにその処理方法 |
EP1453877B1 (en) * | 2001-12-04 | 2007-03-28 | Agfa-Gevaert | Process for preparing an aqueous or non-aqueous solution or dispersion of a polythiophene or thiophene copolymer |
US20050007430A1 (en) * | 2003-03-24 | 2005-01-13 | Therics, Inc. | Method and system of printheads using electrically conductive solvents |
US7537803B2 (en) | 2003-04-08 | 2009-05-26 | New Jersey Institute Of Technology | Polymer coating/encapsulation of nanoparticles using a supercritical antisolvent process |
CN102212251B (zh) * | 2003-04-22 | 2013-06-19 | E.I.内穆尔杜邦公司 | 由聚合物酸性胶体制备的水分散性聚噻吩 |
US7390438B2 (en) * | 2003-04-22 | 2008-06-24 | E.I. Du Pont De Nemours And Company | Water dispersible substituted polydioxythiophenes made with fluorinated polymeric sulfonic acid colloids |
US7247230B2 (en) * | 2003-08-08 | 2007-07-24 | Northeastern University | Electrochemical synthesis and processing of conducting polymers in supercritical media |
FI116626B (fi) | 2004-01-27 | 2006-01-13 | Valtion Teknillinen | Menetelmä johtavien polymeeripinnoitteiden saostamiseksi ylikriittisessä hiilidioksidissa |
US7338620B2 (en) * | 2004-03-17 | 2008-03-04 | E.I. Du Pont De Nemours And Company | Water dispersible polydioxythiophenes with polymeric acid colloids and a water-miscible organic liquid |
JP2006111798A (ja) | 2004-10-18 | 2006-04-27 | Nikkiso Co Ltd | ポリマー微粒子創製方法、およびポリマー微粒子創製装置 |
EP1842586A1 (en) | 2004-11-29 | 2007-10-10 | Japan Science and Technology Agency | Method for preparing composite fine particles |
DE102005016727A1 (de) * | 2005-04-11 | 2006-10-26 | H.C. Starck Gmbh | Elektrolytkondensatoren mit polymerer Außenschicht und Verfahren zu ihrer Herstellung |
DE102005043829A1 (de) | 2005-09-13 | 2007-04-05 | H.C. Starck Gmbh | Verfahren zur Herstellung von Elektrolytkondensatoren mit hoher Nennspannung |
JP5377303B2 (ja) | 2007-06-18 | 2013-12-25 | 英夫 吉田 | 導電性高分子の被膜製造方法 |
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- 2008-03-10 JP JP2008060106A patent/JP5243067B2/ja not_active Expired - Fee Related
- 2008-03-11 US US12/920,989 patent/US8188212B2/en not_active Expired - Fee Related
- 2008-03-11 WO PCT/JP2008/000533 patent/WO2009113125A1/ja active Application Filing
- 2008-03-11 RU RU2010141565/04A patent/RU2462485C2/ru not_active IP Right Cessation
- 2008-03-11 EP EP20080720419 patent/EP2253656B1/en not_active Not-in-force
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EP2253656A4 (en) | 2011-09-28 |
RU2462485C2 (ru) | 2012-09-27 |
US20110071265A1 (en) | 2011-03-24 |
JP5243067B2 (ja) | 2013-07-24 |
US8188212B2 (en) | 2012-05-29 |
JP2009215422A (ja) | 2009-09-24 |
RU2010141565A (ru) | 2012-04-20 |
WO2009113125A1 (ja) | 2009-09-17 |
EP2253656A1 (en) | 2010-11-24 |
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